EP0307933A2 - Ink compositions for ink jet printing - Google Patents
Ink compositions for ink jet printing Download PDFInfo
- Publication number
- EP0307933A2 EP0307933A2 EP88115195A EP88115195A EP0307933A2 EP 0307933 A2 EP0307933 A2 EP 0307933A2 EP 88115195 A EP88115195 A EP 88115195A EP 88115195 A EP88115195 A EP 88115195A EP 0307933 A2 EP0307933 A2 EP 0307933A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- ink composition
- hot melt
- composition according
- resinous binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 107
- 238000007641 inkjet printing Methods 0.000 title claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 50
- 239000011230 binding agent Substances 0.000 claims abstract description 41
- 239000012943 hotmelt Substances 0.000 claims abstract description 21
- 239000003086 colorant Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000000732 arylene group Chemical group 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 6
- 239000000155 melt Substances 0.000 claims abstract description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 4
- 150000004985 diamines Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 150000004665 fatty acids Chemical group 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 20
- 125000005313 fatty acid group Chemical group 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 88
- 239000000758 substrate Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- 239000000975 dye Substances 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 239000000539 dimer Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000013638 trimer Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/34—Hot-melt inks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
Definitions
- This invention relates to resinous binders and more particularly is concerned with ink compositions for ink jet printing.
- Ink jet printing is a well known process for non-contact printing of substrates such as paper, plastic films, metal foils and the like.
- a stream of an ink composition is forced under pressure through a very small orifice by a drive means such as a driven piezoelectric crystal.
- a drive means such as a driven piezoelectric crystal.
- the droplets of the ink composition then receive an electrical charge.
- the charged droplets are deflected causing selected droplets to impinge upon the substrate to be printed in a predetermined pattern to form a dot matrix image of the desired indicia on the substrate.
- ink jet printing apparatus Various types of ink jet printing apparatus are known in the art.
- One of the more common types of ink jet printing apparatus provides a constant discharge of droplets of the ink composition in substantial excess of the amount actually required for printing with the excess droplets being recovered and recycled.
- Another well known type of ink jet printing apparatus is referred to a drop on demand printer. This type of apparatus, as the name indicates, discharges a stream of droplets of the ink composition only when required for printing.
- ink jet printers known in the art and all typically operate on the same general principles as that described above.
- ink jet printing The various types of apparatus used for ink jet printing are relatively well developed from a mechanical standpoint. However, considerable problems are still encountered with ink jet printers. Many of the problems are related to the ink compositions heretofore suggested for use in ink jet printing. Ink compositions which are used in ink jet printing should have certain properties. Initially in dispensing of the ink compositions during printing it is necessary that the ink compositions display a consistant breakup length, drop viscosity, and drop charge under the specific set of conditions employed during the ink jet printing process. To meet this requirement, the ink jet compostion must have stable viscosity and resistive properties and should not dry out upon ageing.
- the ink compositions used for ink jet printing have the usual desired printing properties that can be obtained with inks used in conventional printing processes. These properties include, for example, that the ink composition have satisfactory adhesion to the various of different types of substrates on which it may be printed.
- the indicia which is printed must have a high degree of resolution in order to provide the sharp images required for most printing applications. The ink composition must not rub or smudge on the substrate and the printed indicia should likewise be permanent; that is, of archival quality.
- a further problem in addition to those noted above associated with the presence of volatile solvents in the prior ink compositions used for ink jet printing is that the solvents cause the printed indicia to bleed into the substrates and result in poor resolution.
- the prior art resorted to the expedience of using coated papers which will not be wet out by the ink compositions. This is generally limited in practice, because of the additional cost involved and the requirement in many commercial printing process for "plain paper" printing.
- the use of large amounts of solvents in the ink composition likewise required that the printed substrates be subjected to drying to remove the solvents. In the case of organic solvents this has caused additional health and safety concerns.
- Certain of the prior art ink compositions in addition to containing solvents also contain substantia] amounts of wetting agents to allow the ink composition to wet out and saturate the substrate to be printed. These particular ink compositions tend to excessively wet out the substrates with solvents and in turn cause bleeding with a resulting substantial reduction in the resolution of the printed indicia.
- pigments are used as the colorants. Pigments are preferred to dyes because of the cost, consistent color quality and more importantly becuase of their outstanding permanency.
- problems encountered with the prior art ink compositions used in ink jet printing and particularly because of the drying out of the solvents from prior art ink compositions it has not been possible to successfully use pigments in ink compositions for ink jet printing.
- an ink composition having properties of stability and uniformity of performance under ink jet printing conditions and desired printing properties can be obtained with hot melt ink compositions which have as the binder a polyamide hot melt adhesive which has a low viscosity for example 250 CPS or less at a low melt temperature of for example 150 degrees C.
- hot melt ink compositions consisting of (a) a resinous binder comprised of the compound of the formula wherein R1 represents a polymerized fatty acid residue with two carboxylic acid groups removed, R2 and R3 are the same or different and each represent an alkylene with up to 12 carbon atoms, a cycloalkylene with 6 to 12 carbon atoms, an arylene with 6 to 12 carbon atoms or an alkarylene with 7 to 12 carbon atoms and R4 and R5 are the same or different and each represents an alkyl having up to 36 carbon atoms, a cycloalkyl having up to 36 carbon atoms and aryl having up to 36 carbon atoms or an alkaryl having up to 36 carbon atoms, wherein said resinous binder has a melt viscosity of 250 CPS or less at 150 degrees C and (b) a colorant distributed through the resinous binder in an effective amount sufficient to impart a predetermined color to the resulting
- the essential component of the ink composition of the present invention is preferably a resinous binder which is prepared by the condensation reaction of about one stoichiometric equivalent of polymerized fatty acid, about two stoichiometric equivalent of a diamine and about two stoichiometric equivalent of a monocarboxlic acid.
- the principal product which is obtained as a result of the condensation reaction is itself considered unique and useful aside from its use in the ink composition of this invention.
- the polymerized fatty acids which are used in the preparation of the resinous binder are obtained by the polymerization of olefinically unsaturated monocarboxylic acids containing 16 to 23 carbon atoms, such as oleic acid, linoleic acid, linolenic acid, eleostearic acid and the like.
- Dicarboxylic acids produced in this manner that is, when two moles of the monocarboxylic acid are combined, are referred to as dimer acids.
- Processes for the production of dimer acids are well known to the art.
- C36 dimer acids obtained by the dimerization of an unsaturated C18 acid such as oleic acid, linoleic acid and mixtures thereof (e.g.
- tall oil fatty acids are especially useful and advantageously employed for the preparation of the resinous binder.
- dimer acids have as their principal component a C36 dicarboxylic acid and typically have an acid value in the range 180-215 and neutral equivalent from 265-310. Dimer acids containing less than 30% by weight by-product acids including monobasic acids, trimer acids or higher polymer acids are especially useful for this invention. It is even more advantageous if the dimer acid is hydrogenated prior to use.
- the dimer acids may also be molecularly distilled or otherwise purified to increase the C36 dimer content to 90% or more.
- the second reactant used in the preparation of the resinous binder is a diamine which can be represented by the formula NH2-R6-NH2 wherein R6 represents an alkylene with up to 12 carbon atoms, a cycloalkylene with 6 to 12 carbon atoms, an arylene with 6 to 12 carbon atoms or an alkarylene with 7 to 12 carbon atoms.
- the diamines which are used in this invention are well known in the art as is their preparation and many are readily available commercially.
- the selection of the particular diamine for use in the preparation of the resinous binder of the present invention is dependent upon the properties desired in the ink compositions of the present invention. It should be appreciated that use of different types of diamines in the preparation of the resinous binder will change the temperature and the viscosity at the melt point of the resinous binders which are obtained.
- the most preferred resinous binder used in this invention are prepared with lower alkylene diamines and particularly those having up to 6 carbon atoms. More particularly it has been found that exceptional results are obtained with ethylene diamine or hexamethylene diamine. It is possible to use a mixture of diamines in the preparation of the resinous binder but it has been found that more consistent results from batch to batch are obtained when a single type of diamine is used in the preparation.
- the third reactant used in the preparation of the resinous binder is a monocarboxylic acid of the formula R7-COOH wherein R7 represents an alkyl having up to 36 carbon atoms, a cycloalkyl having up to 36 carbon atoms and aryl having up to 36 carbon atoms or an alkaryl having up to 36 carbon atoms.
- the preferred monocarboxylic acid for use in the preparation of the resinous binder are fatty acids and particularly saturated fatty acid as these acids tend to form resinous binder which are tack free.
- One fatty acid which has been found to be especially useful in this regard is stearic acid as it provides an exceptionally tack free product.
- the preferred method for the preparation of the resinous binder is to conduct the condensation reaction in a series of steps.
- one stoichiometric equivalent of the polymerized fatty acid is reacted with slightly more than two stoichiometric equivalents of the selected diamine or mixture of diamines in the presence of a catalyst such as, phosphoric acid at a temperature of 150 to 200 degrees C until the initial condensation reaction is completed.
- a catalyst such as, phosphoric acid
- An alternate method for the preparation of the resinous binder is to add all of the reactants all at one time.
- the polymerized fatty acids, the diamine reactant, and the monocarboxylic acid reactant are blended together in the presence of catalyst and heated at 150 degrees to 200 degrees C until the reaction is completed. It has been found that the reaction product of this method is substantially the same as that obtained with the sequential addition as noted above. There are however minor amounts of other reaction products which would be anticipated from this particular type of preparation. However the amounts of the addition products are not significant and indeed the additional products appear to somewhat help the overall properties of the ink composition produced in accordance with this method.
- the resinous composition produced in accordance with this invention are characterized by having physical properties which make them especially useful for use in ink jet printing compostions.
- the resinous binders of this invention have a relatively low melting point and consistent low melt viscosity.
- the resinous binders of this invention typically have a viscosity of 250 CPS or less at 150 degrees C which make them especially useful in ink jet printing applications.
- the relatively low viscosity together with the stable properties under ink jet printing condition makes it possible to formulate ink jet compositions without volatile solvents and which can be used over extended periods of time with consistent results. This type of result was not heretofore obtainable with the prior art ink compositions.
- resinous binders of the present invention have exceptional adhesion to a wide variety of substrates including paper, both coated and uncoated, plastic film and metal in the molten (hot melt) state and form exceptional strong bonds to the substrates when solidified.
- a further additional benefit of the resinous binder itself is that because of the presence of the many polyamide linkage the resinous binder is an excellent solvating agent for certain additives including selected types of dyes.
- the resinous binder most preferably used in ink composition are those wherein R2 and R3 are lower alkylene having up to 6 carbon and most preferable are ethylene or hexamethylene and wherein R4 and R5 are saturated alkyl groups with stearyl being the most preferable end group.
- the most preferred resinous binder for use in ink compositions is represented by the formula In printing ink compositions containing the above defined preferred class of resinous binder an expectional combination of stability during ink jet printing, high resolution printing pattern, excellent adhesion to printed substrate and overall excellent print properties are readily obtained.
- the second essential ingredient of the ink jet compositions of this invention is the colorant.
- the generic term colorant is specifically used in this specification in that it is intended to refer to both pigments and dyes which impart a distinct color to the composition used for ink jet printing.
- the purpose of any colorant is to provide contrast between the color of the substrate and the color of ink in order to provide a visually identifiable indicia on the substrate.
- solubilized dyes were solubilized using a volatile solvent in the ink composition which would dissolve the dye so as to be miscible with the resin used as the binder in the ink composition. While soluble dyes do provide adequate colorant in certain situations, they are both less effective and clearly considerably more costly than the pigments typically used with conventional ink composition. This is particularly true with regard to ink compositions which are desired to have archival properties.
- the colorant can be either a dye or a pigment. It has also been found that it is possible to use a combination of both dyes and pigments to obtain a combination effect. In addition many dyes can be effectively used in the composition of the present invention without the use of volatile solvents in that the high concentration of amide linkages in the resinous binder has a significant solvating effect on many dyes.
- the ink compositions of this invention in addition to containing the resinous binder and a colorant can advantageously contain additional conventional additives for imparting certain properties to the ink composition.
- One type of additive which is useful is a solvating agent for the dyes which is nonvolatile at the temperature at which the ink compositions will be printed.
- High melting plasticizer having a melting temperature above the temperature at which the ink composition will be printed can likewise be added to improve the mechanical properties of the ink compositions.
- a still further example of an additive which can be used are materials such as low viscosity waxes and the like which likewise are nonvolatile at the printing temperature to reduce the viscosity of the ink composition.
- Other additives such as agents to modify the conductivity of the ink composition can also be added to the ink composition.
- the ink compositions of this invention are prepared by physically blending together the components used to formulate the composition into a substantially homogeneous mixture.
- the components can be mixed in a finely divided state and then the mixture melted to complete the blending of the components together. It has been found however that it is preferable to initially melt the resinous binder and then blend each of the additives into the molten resinous binder. The resulting molten mixture is then cast into an appropriate size shapes for use a hot melt ink jet printers.
- the ink composition is initially heated in the ink jet printer to a temperature which is somewhat above the melting point of the ink composition but below the temperature at which the components of the ink composition will volatilize or decompose.
- the molten ink composition is then fed into a printing head including heating elements for maintaining the ink composition in the molten state.
- the ink jet printing head is maintained at a predetermined temperature which is preselected for the printing process.
- the ink composition is required to form a printed indicia on a substrate it is dispensed in much the same manner as conventional ink compositions used in ink jet printing.
- the stream of the molten ink composition is forced from the orifice and the droplets form as the ink composition is directed towards the substrate to be printed.
- the molten or semi-molten ink droplets then contact the substrate and adhere to the substrate.
- the temperature is generally selected so that the ink composition will almost immediately solidify on contact with the substrate and bonds to the substrate. No further treatments are required to fix the printing indicia on the substrate. Any ink droplets which are not used in the printing process are recycled to the supply chamber where they are melted and reintroduced into the ink jet printer head. No substantial change has been noted in the performance of the ink composition over an extended period even though a substantial portion of the ink particles are recirculated in the printing process.
- the use of the hot melt ink composition in the ink process prevents the formation of caking or the like at the orifice of the ink jet printers. If upon shutting down the ink jet printer any ink composition is left at the orifices once the ink jet printer is restarted the heating elements in the ink jet printer head cause the deposited solidified ink composition to remelt and be useful in the printing process.
Abstract
Description
- This invention relates to resinous binders and more particularly is concerned with ink compositions for ink jet printing.
- Ink jet printing is a well known process for non-contact printing of substrates such as paper, plastic films, metal foils and the like. In the operation of a typical ink jet printing apparatus a stream of an ink composition is forced under pressure through a very small orifice by a drive means such as a driven piezoelectric crystal. After the stream of the ink composition is forced from the orifice the stream separates into minute uniform size droplets. The droplets of the ink composition then receive an electrical charge. The charged droplets are deflected causing selected droplets to impinge upon the substrate to be printed in a predetermined pattern to form a dot matrix image of the desired indicia on the substrate.
- Various types of ink jet printing apparatus are known in the art. One of the more common types of ink jet printing apparatus provides a constant discharge of droplets of the ink composition in substantial excess of the amount actually required for printing with the excess droplets being recovered and recycled. Another well known type of ink jet printing apparatus is referred to a drop on demand printer. This type of apparatus, as the name indicates, discharges a stream of droplets of the ink composition only when required for printing. There are other types of ink jet printers known in the art and all typically operate on the same general principles as that described above.
- The various types of apparatus used for ink jet printing are relatively well developed from a mechanical standpoint. However, considerable problems are still encountered with ink jet printers. Many of the problems are related to the ink compositions heretofore suggested for use in ink jet printing. Ink compositions which are used in ink jet printing should have certain properties. Initially in dispensing of the ink compositions during printing it is necessary that the ink compositions display a consistant breakup length, drop viscosity, and drop charge under the specific set of conditions employed during the ink jet printing process. To meet this requirement, the ink jet compostion must have stable viscosity and resistive properties and should not dry out upon ageing. One of the major problems encountered with conventional prior art ink compositions is that they contain substantial amounts of either water or organic solvents which upon standing evaporate causing the the ink compositions to dry out and cake. This causes blocking the orifices and considerable other problems in operation of ink jet printers. A further problem is that the loss of the volatile solvents causes the inks to increase in viscosity which will cause substantial changes in the performance of the inks.
- In addition to the unique requirements associated with ink jet printing it is also necessary that the ink compositions used for ink jet printing have the usual desired printing properties that can be obtained with inks used in conventional printing processes. These properties include, for example, that the ink composition have satisfactory adhesion to the various of different types of substrates on which it may be printed. In addition, the indicia which is printed must have a high degree of resolution in order to provide the sharp images required for most printing applications. The ink composition must not rub or smudge on the substrate and the printed indicia should likewise be permanent; that is, of archival quality.
- A further problem in addition to those noted above associated with the presence of volatile solvents in the prior ink compositions used for ink jet printing is that the solvents cause the printed indicia to bleed into the substrates and result in poor resolution. To overcome this, the prior art resorted to the expedience of using coated papers which will not be wet out by the ink compositions. This is generally limited in practice, because of the additional cost involved and the requirement in many commercial printing process for "plain paper" printing. The use of large amounts of solvents in the ink composition likewise required that the printed substrates be subjected to drying to remove the solvents. In the case of organic solvents this has caused additional health and safety concerns.
- Certain of the prior art ink compositions in addition to containing solvents also contain substantia] amounts of wetting agents to allow the ink composition to wet out and saturate the substrate to be printed. These particular ink compositions tend to excessively wet out the substrates with solvents and in turn cause bleeding with a resulting substantial reduction in the resolution of the printed indicia.
- In typical conventional ink compositions for most other printing applications that is aside from ink jet printing, pigments are used as the colorants. Pigments are preferred to dyes because of the cost, consistent color quality and more importantly becuase of their outstanding permanency. However, because of the problems encountered with the prior art ink compositions used in ink jet printing and particularly because of the drying out of the solvents from prior art ink compositions it has not been possible to successfully use pigments in ink compositions for ink jet printing.
- What would be highly desirable would be an ink composition for ink jet printing which would be stable under ink jet printing conditions and which provides excellent print qualities such as high resolution pattern with a high contrast, excellent adhesion to the substrate and also excellent archival properties.
- It has been found that in accordance with the present invention that an ink composition having properties of stability and uniformity of performance under ink jet printing conditions and desired printing properties can be obtained with hot melt ink compositions which have as the binder a polyamide hot melt adhesive which has a low viscosity for example 250 CPS or less at a low melt temperature of for example 150 degrees C. More particularly it has been found that excellent results are obtained with hot melt ink compositions consisting of (a) a resinous binder comprised of the compound of the formula
- The essential component of the ink composition of the present invention is preferably a resinous binder which is prepared by the condensation reaction of about one stoichiometric equivalent of polymerized fatty acid, about two stoichiometric equivalent of a diamine and about two stoichiometric equivalent of a monocarboxlic acid. The principal product which is obtained as a result of the condensation reaction is itself considered unique and useful aside from its use in the ink composition of this invention.
- The polymerized fatty acids which are used in the preparation of the resinous binder are obtained by the polymerization of olefinically unsaturated monocarboxylic acids containing 16 to 23 carbon atoms, such as oleic acid, linoleic acid, linolenic acid, eleostearic acid and the like. Dicarboxylic acids produced in this manner, that is, when two moles of the monocarboxylic acid are combined, are referred to as dimer acids. Processes for the production of dimer acids are well known to the art. C₃₆ dimer acids obtained by the dimerization of an unsaturated C₁₈ acid such as oleic acid, linoleic acid and mixtures thereof (e.g. tall oil fatty acids) are especially useful and advantageously employed for the preparation of the resinous binder. Such dimer acids have as their principal component a C₃₆ dicarboxylic acid and typically have an acid value in the range 180-215 and neutral equivalent from 265-310. Dimer acids containing less than 30% by weight by-product acids including monobasic acids, trimer acids or higher polymer acids are especially useful for this invention. It is even more advantageous if the dimer acid is hydrogenated prior to use. The dimer acids may also be molecularly distilled or otherwise purified to increase the C₃₆ dimer content to 90% or more.
- The second reactant used in the preparation of the resinous binder is a diamine which can be represented by the formula
NH₂-R₆-NH₂
wherein R₆ represents an alkylene with up to 12 carbon atoms, a cycloalkylene with 6 to 12 carbon atoms, an arylene with 6 to 12 carbon atoms or an alkarylene with 7 to 12 carbon atoms. - The diamines which are used in this invention are well known in the art as is their preparation and many are readily available commercially. The selection of the particular diamine for use in the preparation of the resinous binder of the present invention is dependent upon the properties desired in the ink compositions of the present invention. It should be appreciated that use of different types of diamines in the preparation of the resinous binder will change the temperature and the viscosity at the melt point of the resinous binders which are obtained.
- It has been found that the most preferred resinous binder used in this invention are prepared with lower alkylene diamines and particularly those having up to 6 carbon atoms. More particularly it has been found that exceptional results are obtained with ethylene diamine or hexamethylene diamine. It is possible to use a mixture of diamines in the preparation of the resinous binder but it has been found that more consistent results from batch to batch are obtained when a single type of diamine is used in the preparation.
- The third reactant used in the preparation of the resinous binder is a monocarboxylic acid of the formula
R₇-COOH
wherein R₇ represents an alkyl having up to 36 carbon atoms, a cycloalkyl having up to 36 carbon atoms and aryl having up to 36 carbon atoms or an alkaryl having up to 36 carbon atoms. The preferred monocarboxylic acid for use in the preparation of the resinous binder are fatty acids and particularly saturated fatty acid as these acids tend to form resinous binder which are tack free. One fatty acid which has been found to be especially useful in this regard is stearic acid as it provides an exceptionally tack free product. - The preferred method for the preparation of the resinous binder is to conduct the condensation reaction in a series of steps. In the initial step, one stoichiometric equivalent of the polymerized fatty acid is reacted with slightly more than two stoichiometric equivalents of the selected diamine or mixture of diamines in the presence of a catalyst such as, phosphoric acid at a temperature of 150 to 200 degrees C until the initial condensation reaction is completed. Thereafter about two stoichiometric equivalents of the selected monocarboxylic acid or mixture thereof is added to the reaction mixture and the reaction continued until the second condensation reaction is completed.
- An alternate method for the preparation of the resinous binder is to add all of the reactants all at one time. In this particular method the polymerized fatty acids, the diamine reactant, and the monocarboxylic acid reactant are blended together in the presence of catalyst and heated at 150 degrees to 200 degrees C until the reaction is completed. It has been found that the reaction product of this method is substantially the same as that obtained with the sequential addition as noted above. There are however minor amounts of other reaction products which would be anticipated from this particular type of preparation. However the amounts of the addition products are not significant and indeed the additional products appear to somewhat help the overall properties of the ink composition produced in accordance with this method.
- The resinous composition produced in accordance with this invention are characterized by having physical properties which make them especially useful for use in ink jet printing compostions. In particular the resinous binders of this invention have a relatively low melting point and consistent low melt viscosity. The resinous binders of this invention typically have a viscosity of 250 CPS or less at 150 degrees C which make them especially useful in ink jet printing applications. The relatively low viscosity together with the stable properties under ink jet printing condition makes it possible to formulate ink jet compositions without volatile solvents and which can be used over extended periods of time with consistent results. This type of result was not heretofore obtainable with the prior art ink compositions. Additional properties of the resinous binders of the present invention is that they have exceptional adhesion to a wide variety of substrates including paper, both coated and uncoated, plastic film and metal in the molten (hot melt) state and form exceptional strong bonds to the substrates when solidified. A further additional benefit of the resinous binder itself is that because of the presence of the many polyamide linkage the resinous binder is an excellent solvating agent for certain additives including selected types of dyes.
- The resinous binder most preferably used in ink composition are those wherein R₂ and R₃ are lower alkylene having up to 6 carbon and most preferable are ethylene or hexamethylene and wherein R₄ and R₅ are saturated alkyl groups with stearyl being the most preferable end group. The most preferred resinous binder for use in ink compositions is represented by the formula
- The second essential ingredient of the ink jet compositions of this invention is the colorant. The generic term colorant is specifically used in this specification in that it is intended to refer to both pigments and dyes which impart a distinct color to the composition used for ink jet printing. The purpose of any colorant is to provide contrast between the color of the substrate and the color of ink in order to provide a visually identifiable indicia on the substrate. In the prior art, with most ink jet compositions, it was necessary to use solubilized dyes as the colorant. The dyes were solubilized using a volatile solvent in the ink composition which would dissolve the dye so as to be miscible with the resin used as the binder in the ink composition. While soluble dyes do provide adequate colorant in certain situations, they are both less effective and clearly considerably more costly than the pigments typically used with conventional ink composition. This is particularly true with regard to ink compositions which are desired to have archival properties.
- It has been found within the compositions of the present invention the colorant can be either a dye or a pigment. It has also been found that it is possible to use a combination of both dyes and pigments to obtain a combination effect. In addition many dyes can be effectively used in the composition of the present invention without the use of volatile solvents in that the high concentration of amide linkages in the resinous binder has a significant solvating effect on many dyes.
- The ink compositions of this invention in addition to containing the resinous binder and a colorant can advantageously contain additional conventional additives for imparting certain properties to the ink composition. One type of additive which is useful is a solvating agent for the dyes which is nonvolatile at the temperature at which the ink compositions will be printed. High melting plasticizer having a melting temperature above the temperature at which the ink composition will be printed can likewise be added to improve the mechanical properties of the ink compositions. A still further example of an additive which can be used are materials such as low viscosity waxes and the like which likewise are nonvolatile at the printing temperature to reduce the viscosity of the ink composition. Other additives such as agents to modify the conductivity of the ink composition can also be added to the ink composition.
- The ink compositions of this invention are prepared by physically blending together the components used to formulate the composition into a substantially homogeneous mixture. The components can be mixed in a finely divided state and then the mixture melted to complete the blending of the components together. It has been found however that it is preferable to initially melt the resinous binder and then blend each of the additives into the molten resinous binder. The resulting molten mixture is then cast into an appropriate size shapes for use a hot melt ink jet printers.
- In the use of the ink compositions of the present invention the ink composition is initially heated in the ink jet printer to a temperature which is somewhat above the melting point of the ink composition but below the temperature at which the components of the ink composition will volatilize or decompose. The molten ink composition is then fed into a printing head including heating elements for maintaining the ink composition in the molten state. The ink jet printing head is maintained at a predetermined temperature which is preselected for the printing process. As the ink composition is required to form a printed indicia on a substrate it is dispensed in much the same manner as conventional ink compositions used in ink jet printing. The stream of the molten ink composition is forced from the orifice and the droplets form as the ink composition is directed towards the substrate to be printed. The molten or semi-molten ink droplets then contact the substrate and adhere to the substrate. The temperature is generally selected so that the ink composition will almost immediately solidify on contact with the substrate and bonds to the substrate. No further treatments are required to fix the printing indicia on the substrate. Any ink droplets which are not used in the printing process are recycled to the supply chamber where they are melted and reintroduced into the ink jet printer head. No substantial change has been noted in the performance of the ink composition over an extended period even though a substantial portion of the ink particles are recirculated in the printing process. In addition, it has been found that the use of the hot melt ink composition in the ink process prevents the formation of caking or the like at the orifice of the ink jet printers. If upon shutting down the ink jet printer any ink composition is left at the orifices once the ink jet printer is restarted the heating elements in the ink jet printer head cause the deposited solidified ink composition to remelt and be useful in the printing process.
Claims (23)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/098,447 US4830671A (en) | 1987-09-18 | 1987-09-18 | Ink compositions for ink jet printing |
US98447 | 1987-09-18 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0307933A2 true EP0307933A2 (en) | 1989-03-22 |
EP0307933A3 EP0307933A3 (en) | 1990-09-19 |
EP0307933B1 EP0307933B1 (en) | 1992-11-19 |
Family
ID=22269321
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88115195A Expired EP0307933B1 (en) | 1987-09-18 | 1988-09-16 | Ink compositions for ink jet printing |
Country Status (4)
Country | Link |
---|---|
US (1) | US4830671A (en) |
EP (1) | EP0307933B1 (en) |
JP (1) | JPH0674393B2 (en) |
DE (1) | DE3876049T2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0385452A1 (en) * | 1989-03-03 | 1990-09-05 | Willi Möller AG | Carboxylic acid amides which form lipophilic complexes with magnesium ions, method for preparation of the lipophilic magnesium complexes and ion selective components |
US5496879A (en) * | 1992-02-25 | 1996-03-05 | Siegwerk Druckfarben Gmbh & Co. Kg | Printing ink |
WO2000078878A2 (en) * | 1999-06-24 | 2000-12-28 | Arizona Chemical Company | Ink jet printing compositions containing ester-terminated dimer acid-based oligo(ester/amide) |
EP1069164A1 (en) * | 1999-07-16 | 2001-01-17 | Xerox Corporation | A composition of matter, a phase change ink, and a method of reducing a coefficient of friction of a phase change ink formulations |
WO2001087847A2 (en) * | 2000-05-16 | 2001-11-22 | Arizona Chemical Company | Polyalkyleneoxydiamine polyamides useful for formulating inks for phase-change jet printing |
WO2004106442A2 (en) * | 2003-05-22 | 2004-12-09 | Arizona Chemical Company | Cyclic bisamides useful in formulating inks for phase-change printing |
Families Citing this family (96)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5279652A (en) * | 1988-03-24 | 1994-01-18 | Rainer Kaufmann | Use of solids as antiblocking additives for marker liquids |
US4889560A (en) * | 1988-08-03 | 1989-12-26 | Tektronix, Inc. | Phase change ink composition and phase change ink produced therefrom |
US5006170A (en) * | 1989-06-22 | 1991-04-09 | Xerox Corporation | Hot melt ink compositions |
WO1991010710A1 (en) * | 1990-01-22 | 1991-07-25 | Spectra, Inc. | Black ink for ink jet systems |
US5108505A (en) * | 1990-05-16 | 1992-04-28 | Hewlett-Packard Company | Waterfast inks via cyclodextrin inclusion complex |
US5372852A (en) * | 1992-11-25 | 1994-12-13 | Tektronix, Inc. | Indirect printing process for applying selective phase change ink compositions to substrates |
US5389958A (en) * | 1992-11-25 | 1995-02-14 | Tektronix, Inc. | Imaging process |
US5902841A (en) * | 1992-11-25 | 1999-05-11 | Tektronix, Inc. | Use of hydroxy-functional fatty amides in hot melt ink jet inks |
US5354368A (en) * | 1993-05-04 | 1994-10-11 | Markem Corporation | Hot melt jet ink composition |
US5597856A (en) * | 1993-09-24 | 1997-01-28 | Dataproducts Corporation | Hot melt ink for transparency applications |
US5421868A (en) * | 1993-12-28 | 1995-06-06 | International Business Machines Corporation | Ink composition |
US5507864A (en) * | 1994-11-14 | 1996-04-16 | Tektronix, Inc. | Phase change ink composition employing a combination of dyes |
US5645632A (en) * | 1996-02-14 | 1997-07-08 | Union Camp Corporation | Diesters of polymerized fatty acids useful in formulating hot-melt inks |
US6063834A (en) * | 1997-12-08 | 2000-05-16 | Lexmark International, Inc. | Wet-rub resistant ink compositions |
US6476122B1 (en) | 1998-08-20 | 2002-11-05 | Vantico Inc. | Selective deposition modeling material |
US6132665A (en) | 1999-02-25 | 2000-10-17 | 3D Systems, Inc. | Compositions and methods for selective deposition modeling |
US6395811B1 (en) | 1999-11-11 | 2002-05-28 | 3D Systems, Inc. | Phase change solid imaging material |
US6133353A (en) * | 1999-11-11 | 2000-10-17 | 3D Systems, Inc. | Phase change solid imaging material |
US6870011B2 (en) * | 2001-01-24 | 2005-03-22 | Arizona Chemical Company | Hydrocarbon-terminated polyether-polyamide block copolymers and uses thereof |
US6399713B1 (en) | 2001-01-24 | 2002-06-04 | Arizona Chemical Company | Hydrocarbon-terminated polyether-polyamide block copolymers and uses thereof |
US6552160B2 (en) | 2001-05-14 | 2003-04-22 | Arizona Chemical Company | Ester-terminated poly(ester-amides) useful for formulating transparent gels in low polarity fluids |
US6585816B1 (en) | 2001-11-09 | 2003-07-01 | Xerox Corporation | Phase change inks containing borate esters |
US6860930B2 (en) * | 2003-06-25 | 2005-03-01 | Xerox Corporation | Phase change inks containing branched triamides |
US6946025B2 (en) * | 2003-10-22 | 2005-09-20 | Xerox Corporation | Process for preparing tetra-amide compounds |
US6989052B1 (en) * | 2004-06-30 | 2006-01-24 | Xerox Corporation | Phase change ink printing process |
US7758268B2 (en) * | 2005-12-20 | 2010-07-20 | Xerox Corporation | Hand held photochromic marking implement |
US20080057233A1 (en) * | 2006-08-29 | 2008-03-06 | Harrison Daniel J | Conductive thermal transfer ribbon |
US7829162B2 (en) | 2006-08-29 | 2010-11-09 | international imagining materials, inc | Thermal transfer ribbon |
US20080098927A1 (en) * | 2006-10-26 | 2008-05-01 | Xerox Corporation | Pigmented phase change inks |
US7786209B2 (en) * | 2006-10-27 | 2010-08-31 | Xerox Corporation | Nanostructured particles, phase change inks including same and methods for making same |
US20080145557A1 (en) | 2006-12-18 | 2008-06-19 | Xerox Corporation | Phase change inks containing dialkyl ethers |
US20080187664A1 (en) | 2007-02-06 | 2008-08-07 | Xerox Corporation | Phase change inks containing colorant compounds |
US7736426B2 (en) * | 2007-02-06 | 2010-06-15 | Xerox Corporation | Phase change inks containing colorant compounds |
US7997712B2 (en) * | 2007-02-06 | 2011-08-16 | Xerox Corporation | Phase change inks containing colorant compounds |
US8163074B2 (en) | 2007-02-06 | 2012-04-24 | Xerox Corporation | Phase change inks containing colorant compounds |
US7749315B2 (en) * | 2007-04-04 | 2010-07-06 | Xerox Corporation | Phase change inks containing colorant compounds |
US7811368B2 (en) * | 2007-04-04 | 2010-10-12 | Xerox Corporation | Phase change inks containing colorant compounds |
US7677713B2 (en) | 2007-05-30 | 2010-03-16 | Xerox Corporation | Solid ink set incorporating naturally derived materials and processes thereof |
US7473310B2 (en) * | 2007-06-07 | 2009-01-06 | Xerox Corporation | Nanosized particles of monoazo laked pigment and non-aqueous compositions containing same |
US7427324B1 (en) | 2007-06-07 | 2008-09-23 | Xerox Corporation | Methods of making quinacridone nanoscale pigment particles |
US7834072B2 (en) * | 2007-06-07 | 2010-11-16 | Xerox Corporation | Non-aqueous compositions containing nanosized particles of monoazo laked pigment |
US7465349B1 (en) | 2007-06-07 | 2008-12-16 | Xerox Corporation | Method of making nanosized particles of monoazo laked pigment |
US7649026B2 (en) * | 2007-06-07 | 2010-01-19 | Xerox Corporation | Radiation curable compositions containing nanosized particles of monoazo laked pigment |
US7470320B1 (en) * | 2007-06-07 | 2008-12-30 | Xerox Corporation | Nanosized particles of monoazo laked pigment with tunable properties |
US7427323B1 (en) | 2007-06-07 | 2008-09-23 | Xerox Corporation | Quinacridone nanoscale pigment particles |
US7465348B1 (en) | 2007-06-07 | 2008-12-16 | Xerox Corporation | Nanosized particles of monoazo laked pigment |
US8791202B2 (en) * | 2007-09-21 | 2014-07-29 | Xerox Corporation | Phase change ink compositions |
US20090097898A1 (en) * | 2007-10-16 | 2009-04-16 | Xerox Corporation | Hand held photochromic marking implement |
US7985290B2 (en) * | 2008-03-07 | 2011-07-26 | Xerox Corporation | Nonpolar liquid and solid phase change ink compositions comprising nanosized particles of benzimidazolone pigments |
US8025723B2 (en) | 2008-03-07 | 2011-09-27 | Xerox Corporation | Nonpolar liquid and solid phase change ink compositions comprising nanosized particles of benzimidazolone pigments |
US7857901B2 (en) | 2008-03-07 | 2010-12-28 | Xerox Corporation | Nonpolar liquid and solid phase change ink compositions comprising nanosized particles of benzimidazolone pigments |
US8603235B2 (en) | 2008-04-03 | 2013-12-10 | Xerox Corporation | Phase change inks containing Fischer-Tropsch waxes |
US7534294B1 (en) | 2008-04-14 | 2009-05-19 | Xerox Corporation | Quinacridone nanoscale pigment particles and methods of making same |
US20090297714A1 (en) * | 2008-06-02 | 2009-12-03 | Xerox Corporation | Flush pigment for solid inkjet ink |
US7563318B1 (en) | 2008-07-02 | 2009-07-21 | Xerox Corporation | Method of making nanoscale particles of AZO pigments in a microreactor or micromixer |
US8123344B2 (en) | 2008-08-04 | 2012-02-28 | Xerox Corporation | Ink carriers containing surface modified nanoparticles, phase change inks including same, and methods for making same |
US7537654B1 (en) | 2008-09-15 | 2009-05-26 | Xerox Corporation | Quinacridone nanoscale pigment particles and methods of making same |
US8029861B2 (en) * | 2008-09-23 | 2011-10-04 | Xerox Corporation | Ink carriers containing low viscosity functionalized waxes, phase change inks including same, and methods for making same |
US8586141B2 (en) * | 2008-10-06 | 2013-11-19 | Xerox Corporation | Fluorescent solid ink made with fluorescent nanoparticles |
US8236198B2 (en) * | 2008-10-06 | 2012-08-07 | Xerox Corporation | Fluorescent nanoscale particles |
US8541154B2 (en) * | 2008-10-06 | 2013-09-24 | Xerox Corporation | Toner containing fluorescent nanoparticles |
US8222313B2 (en) * | 2008-10-06 | 2012-07-17 | Xerox Corporation | Radiation curable ink containing fluorescent nanoparticles |
US8147714B2 (en) * | 2008-10-06 | 2012-04-03 | Xerox Corporation | Fluorescent organic nanoparticles and a process for producing fluorescent organic nanoparticles |
US8177897B2 (en) * | 2008-11-17 | 2012-05-15 | Xerox Corporation | Phase change inks containing graphene-based carbon allotrope colorants |
US20100122642A1 (en) * | 2008-11-17 | 2010-05-20 | Xerox Corporation | Inks including carbon nanotubes dispersed in a polymer matrix |
US8348409B2 (en) * | 2008-11-17 | 2013-01-08 | Xerox Corporation | Ink jet inks containing nanodiamond black colorants |
US7985286B2 (en) * | 2008-11-24 | 2011-07-26 | Xerox Corporation | Solid inks with lower coefficient of friction |
US8101801B2 (en) | 2009-05-18 | 2012-01-24 | Xerox Corporation | Low molecular weight quaternary ammonium salt dispersants |
US8118922B2 (en) * | 2009-05-18 | 2012-02-21 | Xerox Corporation | Pigmented phase change inks containing low molecular weight quaternary ammonium salt dispersants |
US8915993B2 (en) * | 2009-06-10 | 2014-12-23 | Xerox Corporation | Solid or phase change inks with improved properties |
US8002399B2 (en) * | 2009-12-02 | 2011-08-23 | Xerox Corporation | Solid inks incorporating a polyhydroxyalkanoate compound for enhanced properties |
US20110177245A1 (en) | 2010-01-19 | 2011-07-21 | Xerox Corporation | Ink compositions |
US8652575B2 (en) * | 2010-01-19 | 2014-02-18 | Xerox Corporation | Ink compositions |
US8123848B2 (en) | 2010-05-03 | 2012-02-28 | Xerox Corporation | Fluorescent ink compositions and fluorescent particles |
US8367020B2 (en) | 2010-08-05 | 2013-02-05 | Xerox Corporation | Hydroxyl group-containing solid inks |
US8277032B2 (en) | 2010-08-05 | 2012-10-02 | Xerox Corporation | Acidic group-containing solid inks |
US8449096B2 (en) | 2010-12-06 | 2013-05-28 | Xerox Corporation | Five member ring stabilizers for quinacridone-type pigments in solid ink |
US8544998B2 (en) | 2010-12-16 | 2013-10-01 | Xerox Corporation | Solid inks containing ketone waxes and branched amides |
US8450385B2 (en) | 2010-12-21 | 2013-05-28 | Xerox Corporation | Urea-urethane gellant compositions with controlled molecular weight and methods of preparation |
US8544999B2 (en) | 2010-12-22 | 2013-10-01 | Xerox Corporation | Phase change magnetic ink and process for preparing same |
US8360546B2 (en) | 2010-12-22 | 2013-01-29 | Xerox Corporation | Phase change magnetic ink and process for preparing same |
US8702217B2 (en) | 2011-03-17 | 2014-04-22 | Xerox Corporation | Phase change magnetic ink comprising polymer coated magnetic nanoparticles and process for preparing same |
US8646896B2 (en) | 2011-03-17 | 2014-02-11 | Xerox Corporation | Phase change magnetic ink comprising surfactant coated magnetic nanoparticles and process for preparing same |
US8657431B2 (en) | 2011-03-17 | 2014-02-25 | Xerox Corporation | Phase change magnetic ink comprising carbon coated magnetic nanoparticles and process for preparing same |
US8714723B2 (en) * | 2011-05-11 | 2014-05-06 | Xerox Corporation | Robust curable solid inks and methods for using the same |
US8581000B2 (en) | 2011-06-06 | 2013-11-12 | Xerox Corporation | Process for preparing amide gellant compounds with aromatic end groups |
US8980406B2 (en) | 2012-08-28 | 2015-03-17 | 3D Systems, Inc. | Color stable inks and applications thereof |
US9657186B2 (en) | 2012-09-13 | 2017-05-23 | 3D Systems, Inc. | Opaque inks and applications thereof |
US8714724B2 (en) | 2012-10-02 | 2014-05-06 | Xerox Corporation | Phase change inks containing novel synergist |
US8696100B1 (en) | 2012-10-02 | 2014-04-15 | Xerox Corporation | Phase change ink containing synergist for pigment dispersion |
US8974047B2 (en) | 2012-11-27 | 2015-03-10 | Xerox Corporation | Phase change ink containing ethylene vinyl acetate |
US8647422B1 (en) | 2012-11-30 | 2014-02-11 | Xerox Corporation | Phase change ink comprising a modified polysaccharide composition |
US8616693B1 (en) | 2012-11-30 | 2013-12-31 | Xerox Corporation | Phase change ink comprising colorants derived from plants and insects |
US9228099B2 (en) | 2012-12-21 | 2016-01-05 | Xerox Corporation | Phase change ink composition and process for preparing same |
US9090777B2 (en) | 2013-04-04 | 2015-07-28 | Xerox Corporation | Low cost process for solid ink using dry flushed pigments |
US9157002B2 (en) | 2013-07-12 | 2015-10-13 | Xerox Corporation | Phase change ink pigment dispersion process |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3412115A (en) * | 1964-11-02 | 1968-11-19 | Gen Mills Inc | Polyamide resin |
US3872044A (en) * | 1972-09-25 | 1975-03-18 | Ferro Corp | Thermoplastic screen process inks |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4843960A (en) * | 1971-10-08 | 1973-06-25 | ||
JPS5554368A (en) * | 1978-10-17 | 1980-04-21 | Canon Inc | Recording medium solid at room temperature, and method of recording using the same |
US4256818A (en) * | 1979-11-05 | 1981-03-17 | Xerox Corporation | Magnetic or electrostatographic imaging and high speed fusing method uses polyamide resin in toner |
DE3243794A1 (en) * | 1982-11-26 | 1984-05-30 | Schering AG, 1000 Berlin und 4709 Bergkamen | ALCOHOL SOLE PRINTING INKS |
US4514540A (en) * | 1983-09-26 | 1985-04-30 | Union Camp Corporation | Water reducible polyamides |
US4508868A (en) * | 1984-03-29 | 1985-04-02 | Henkel Corporation | Polymeric fat acid polyamide resins for use in flexographic ink vehicles having reduced solvent emissions |
JPH07115470B2 (en) * | 1984-05-10 | 1995-12-13 | ウイレツト インターナシヨナル リミテツド | Molten thermoplastic composition and method of applying the composition to a substrate |
JPS62295973A (en) * | 1985-08-01 | 1987-12-23 | Seiko Epson Corp | Printer ink |
-
1987
- 1987-09-18 US US07/098,447 patent/US4830671A/en not_active Expired - Lifetime
-
1988
- 1988-09-16 DE DE8888115195T patent/DE3876049T2/en not_active Expired - Lifetime
- 1988-09-16 EP EP88115195A patent/EP0307933B1/en not_active Expired
- 1988-09-16 JP JP63230226A patent/JPH0674393B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3412115A (en) * | 1964-11-02 | 1968-11-19 | Gen Mills Inc | Polyamide resin |
US3872044A (en) * | 1972-09-25 | 1975-03-18 | Ferro Corp | Thermoplastic screen process inks |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0385452A1 (en) * | 1989-03-03 | 1990-09-05 | Willi Möller AG | Carboxylic acid amides which form lipophilic complexes with magnesium ions, method for preparation of the lipophilic magnesium complexes and ion selective components |
US5496879A (en) * | 1992-02-25 | 1996-03-05 | Siegwerk Druckfarben Gmbh & Co. Kg | Printing ink |
US6350889B1 (en) | 1999-06-24 | 2002-02-26 | Arizona Chemical Company | Ink jet printing compositions containing ester-terminated dimer acid-based oligo (ester/amide) |
WO2000078878A2 (en) * | 1999-06-24 | 2000-12-28 | Arizona Chemical Company | Ink jet printing compositions containing ester-terminated dimer acid-based oligo(ester/amide) |
WO2000078878A3 (en) * | 1999-06-24 | 2001-07-12 | Int Paper Co | Ink jet printing compositions containing ester-terminated dimer acid-based oligo(ester/amide) |
EP1069164A1 (en) * | 1999-07-16 | 2001-01-17 | Xerox Corporation | A composition of matter, a phase change ink, and a method of reducing a coefficient of friction of a phase change ink formulations |
WO2001087847A2 (en) * | 2000-05-16 | 2001-11-22 | Arizona Chemical Company | Polyalkyleneoxydiamine polyamides useful for formulating inks for phase-change jet printing |
WO2001087847A3 (en) * | 2000-05-16 | 2002-05-16 | Arizona Chem | Polyalkyleneoxydiamine polyamides useful for formulating inks for phase-change jet printing |
US6492458B1 (en) | 2000-05-16 | 2002-12-10 | Arizona Chemical Company | Polyalkyleneoxydiamine polyamides useful for formulating inks for phase-change jet printing |
WO2004106442A2 (en) * | 2003-05-22 | 2004-12-09 | Arizona Chemical Company | Cyclic bisamides useful in formulating inks for phase-change printing |
WO2004106442A3 (en) * | 2003-05-22 | 2005-09-15 | Arizona Chem | Cyclic bisamides useful in formulating inks for phase-change printing |
US6960248B2 (en) | 2003-05-22 | 2005-11-01 | Arizona Chemical Company | Cyclic bisamides useful in formulating inks for phase-change printing |
CN100560662C (en) * | 2003-05-22 | 2009-11-18 | 阿利桑那化学公司 | Be used to prepare the ring-type bisamide of phase change printing-ink |
CN101423683B (en) * | 2003-05-22 | 2010-12-01 | 阿利桑那化学公司 | Cyclic bisamides useful in formulating inks for phase-change printing |
US8269046B2 (en) | 2003-05-22 | 2012-09-18 | Arizona Chemical Company, Llc | Cyclic bisamides useful in formulating inks for phase-change printing |
Also Published As
Publication number | Publication date |
---|---|
JPH0674393B2 (en) | 1994-09-21 |
JPH01104676A (en) | 1989-04-21 |
US4830671A (en) | 1989-05-16 |
DE3876049T2 (en) | 1993-05-27 |
EP0307933A3 (en) | 1990-09-19 |
EP0307933B1 (en) | 1992-11-19 |
DE3876049D1 (en) | 1992-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0307933B1 (en) | Ink compositions for ink jet printing | |
US5194638A (en) | Resinous binders for use in ink compositions for ink jet printing | |
EP1514912B1 (en) | Phase change inks containing branched triamides | |
US6174937B1 (en) | Composition of matter, a phase change ink, and a method of reducing a coefficient of friction of a phase change ink formulation | |
EP0880563B1 (en) | Diesters of polymerized fatty acids useful in formulating hot-melt inks | |
EP1916281B1 (en) | Phase Change Inks | |
JP3053589B2 (en) | Aqueous inkjet ink composition | |
US5074915A (en) | Printing inks | |
JPH054992B2 (en) | ||
JP3180619B2 (en) | Phase change aqueous ink composition | |
DE2534845A1 (en) | PRINTING PROCESS AND SUITABLE MELT PRINTING INKS | |
AU669203B2 (en) | Printing inks and method of ink jet printing | |
SE437997B (en) | NON-WATERLY BOTTOM BLACK COMPOSITION WITH HIGH TORQUE CONTENT | |
DE60311917T2 (en) | Ink composition for fusible ink | |
DE69636069T2 (en) | INK FOR INK JET PRESSURE | |
DE2365051B2 (en) | Process for the production of modified hydrocarbon resins for printing inks | |
JPH06507651A (en) | Inkjet compositions and inkjet methods | |
EP0798351B1 (en) | Printed article and method | |
US8974047B2 (en) | Phase change ink containing ethylene vinyl acetate | |
DE2635226C2 (en) | Printing processes and suitable melt printing inks | |
CA1049705A (en) | Jet ink compositions | |
Pekarovicova et al. | Phase-change inks | |
DE3510415A1 (en) | USE OF POLYAMIDE RESIN FOR RELIEF PRINTING | |
EP1520885B1 (en) | Process and compositions for printing | |
KR100355466B1 (en) | Hot-melted color ink composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE FR GB IT NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19901119 |
|
17Q | First examination report despatched |
Effective date: 19910916 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL |
|
ET | Fr: translation filed | ||
REF | Corresponds to: |
Ref document number: 3876049 Country of ref document: DE Date of ref document: 19921224 |
|
ITF | It: translation for a ep patent filed |
Owner name: SOCIETA' ITALIANA BREVETTI S.P.A. |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
NLS | Nl: assignments of ep-patents |
Owner name: ARIZONA CHEMICAL COMPANY A DELAWARE CORPORATION Effective date: 20070522 Owner name: INTERNATIONAL PAPER COMPANY Effective date: 20070522 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
BECA | Be: change of holder's address |
Owner name: *AEIZONA CHEMICAL CY4600 TOUCHTON ROAD.E., JACKSON Effective date: 20070329 |
|
BECH | Be: change of holder |
Owner name: *AEIZONA CHEMICAL CY Effective date: 20070329 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20070926 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20070927 Year of fee payment: 20 Ref country code: NL Payment date: 20070923 Year of fee payment: 20 Ref country code: DE Payment date: 20071031 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20071025 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20070917 Year of fee payment: 20 |
|
BE20 | Be: patent expired |
Owner name: *AEIZONA CHEMICAL CY Effective date: 20080916 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20080915 |
|
NLV7 | Nl: ceased due to reaching the maximum lifetime of a patent |
Effective date: 20080916 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20080916 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20080915 |